Density Functional Theory Study of the Mechanisms and Stereochemistry of the Rh(I)-Catalyzed Intramolecular [3+2] Cycloadditions of 1-Ene- and 1-Yne-Vinylcyclopropanes.
The mechanisms, structures of all stationary points involved, and kinetic and thermodynamic parameters of the Rh(l)-catalyzed intramolecular [3+2] cycloaddition reactions of 1-eneand 1-yne-vinylcyclopropanes (1-ene-VCPs and 1-yne-VCP5) have been investigated using density functional theory (DFT) cal...
| Publicado en: | Journal of the American Chemical Society Vol. 133; no. 3; pp. 447 - 462 |
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| Autores principales: | , , |
| Formato: | Artículo |
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American Chemical Society
1/26/2011
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=58545164&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 58545164 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 1/26/2011 vid: 133 iid: 3 pid: 997 pub: American Chemical Society artinfo: ui: 58545164 10.1021/ja107396t ppf: 447 ppct: 15 formats: tig: atl: Density Functional Theory Study of the Mechanisms and Stereochemistry of the Rh(I)-Catalyzed Intramolecular [3+2] Cycloadditions of 1-Ene- and 1-Yne-Vinylcyclopropanes. aug: au: Lei Jiao Mu Lin Zhi-Xiang Yu affil: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China su: Ring formation (Chemistry) Stereochemistry Density functionals Organic synthesis Alkenes Cyclopropane Hydrides sug: subj: Ring formation (Chemistry) Stereochemistry Density functionals Organic synthesis Alkenes Cyclopropane Hydrides ab: The mechanisms, structures of all stationary points involved, and kinetic and thermodynamic parameters of the Rh(l)-catalyzed intramolecular [3+2] cycloaddition reactions of 1-eneand 1-yne-vinylcyclopropanes (1-ene-VCPs and 1-yne-VCP5) have been investigated using density functional theory (DFT) calculations. The computational results showed that the [3+2] reactions of 1-ene/yne-VCPs studied here occur through a catalytic cycle of substrate-catalyst complex formation, cyclopropane cleavage, alkene/alkyne insertion, and reductive elimination. Alkene/alkyne insertion is the rateand stereoselectivitydetermining step of these multistep [3+2] cycloadditions. The experimentally observed high reactivity of 1-yne-VCPs compared to 1-ene-VCPs is well rationalized by the differences of steric effects in the alkyne/ alkene insertion transition states. DFT calculations unveiled that the relative orientation of the tethers in the 1 -ene/yne-VCPs plays a key role in controlling the stereochemistry of the [3+2] cycloadducts. In addition, DFT calculation results are used to explain why, in some cases, the formation of the fl-hydride elimination byproduct can compete with the [3+2] pathway. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2011 holdings: @attributes: islocal: N |
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